Monoazo dyestuffs insoluble in water



Patented Nov. 26, 1940 PATENT OFFICE 2,222,763 MONOAZO prns rgirrs INSQLUBLE IN TEE Ernst Fischer, Offenbach-on-the-Main, Germany,

assignor to General Aniline & Film Corporation, a corporation of Delaware No Drawings, Application June 24, 1939, Serial No.28 0,973. In Germany June25, 1938 l 5 Claims.

The present invention relates to monoazodyestuffs insoluble in water; more particularly, it relates to dyestuffs of the following general formula:

C 0 .NH.aryl

wherein the benzene radical a may be further substituted by alkyl-, alkoxy-, aryloxy-groups or halogen, X means the group -CO or -SO2, R1 and R2 being alkyl-, aralkyl-, arylor hydroaromatic radicals which may be connected in a heterocyclic ring system, with the proviso that if X stands for S02, R1 and R2 may only be simultaneously alkyl radicals, if the sum of their carbon atoms be at least 5, and Z stands for a carbazole, diphenylene oxide or diphenylene sulfide,

radical.

I have found that valuable pigment dyestuffs may be obtained by coupling the diazo-compound from an amine of the general formula:

wherein the benzene radical or may be further substituted by alkyl-, alkoxy-, aryloxy-groupsor halogen, X means the group CO or SO2--, R1 and R2 being alkyl-, aralkyl-arylor hydroaromatic radicals which may be connected in a heterocyclic ring system, with the proviso that if X stands for $02,121 and R2 may only be simultaneously alkyl radicals, if the sum of their carbon atoms be at least 5,

with an arylide of 2-hydroxycarbazole-3-carboxylic acid, B-hydroxydiphenylene oxide-2-carboxylic acid or B-hydroxyldiphenylene sulfide-2- carboxylic acid, only such dyestuff components being used as do not contain any group lending solubility in water, such as the sulfonic or 'carboxylic acid group.

The new dyestuffs yield generally brown tints which, depending upon the kind of the diazocompound used, extend to black-brown and have good properties of fastness. They are insoluble in water, but very easily soluble in many organic solvents, for instance, hydrocarbons, alcohols, esters, ketones and can be used for coloring these solvents as well as the lacquers prepared by means of these solvents, such as nitroor acetylcellulose lacquers, films or plastic masses. They are also very suitable for coloring varnishes, candles and fats.

In comparison with the dyestuffs described in German Patents Nos. 551,880, 594,326 and 596,- 753, the dyestuffs obtainable by this invention are distinguished by their enhanced solubility in organic solvents so that they are very'suitable for coloring these solvents as well as the lacquers prepared by means of these solvents, such as nitroor acetyl-cellulose lacquers, films or artificial masses, and also for coloring varnishes, candles and fats whereas the dyestuffs of the above-named Germanpatents have either no solubility inorganic solvents or a solubility too smallfor these purposes.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto; the parts are by weight:

1. 9.6 parts of l-aminobenzene-Z-(carbonyldiethylamine) are diazotized in the usual manner. In order to bind the excess of mineral acid sodium acetate is added to the diazo-solution and the whole is stirred into a solution of 15.1

, parts of 2-hydroxycarbazole-3-(carbonyl-aminobenzene) in dilute caustic soda solution. When the coupling is finished the dyestuff formed is filtered with suction, washed well and dried. It is a brown powder which dissolves easily in butyl acetate, acetone, xylene and other organic solvents and colors cellulose ester lacquers brown tints of good properties of fastness.

The dyestuff corresponds with the following formula:

3. By using in Example 1 instead of 15.1 parts of 2-hydroxycarbazole-3 (carbonyl aminobenzene), 18.2 parts of 3-hydroxydiphenylene oxide- 2-(carbonyl-Y-amino-Z'fi dimethoxybenzene), a dyestuff of similarly good properties of fastness is obtained which colors the various organic solvents and the lacquers prepared therewith, and also candles and fats, brown tints.

4.. From the diazo-compound of 15.9 parts of 1- aminobenzene 2- (sulfonyl-N- (n) -butyl-1'-amino-2'-methylbenzene) and 17.6 parts of 2-hydroxycarbazole-fi-(carbonyl 2' aminonaphthalene) there is obtained, in the manner described in Examples 1 and 2, a brown pigment dyestuff which is easily soluble in organic solvents and colors artificial masses and lacquers prepared therewith, also candles and.fats, yellowish-brown tints of good fastness to light.

The following table illustrates a number of other mono-azo-dyestufis obtainable by this invention, which are likewise easily soluble in the solventsusually applied for these purposes and have good properties of fastness:

1. The water-insoluble mono-azo-dyestuffs of the following general formula:

C O.NH.Y

group consisting of alkyl, benzyl, radicals of the benzene and naphthalene series and hydroaromatic radicals which may be, connected in a heterocyclic ring system, with the proviso that if X stands for S02, R1 and R2 may, only be simultaneously alkyl radicals if the sum of their carbon atoms be at least 5, Z stands for a radical of the group consisting of carbazole, diphenylene oxide and diphenylene sulfide and Y stands for a member of the group consisting of radicals of the benzene and naphthalene series, being insoluble in water, but very easily soluble in organic solvents and yielding generally brown tints of good properties of fastness.

Diem-compound from. Coupled with Shade 2-hydroxycarbazole-3-(carbonyl- ,l 1- arnm)obenzene -2-(carbonyl N -ethyl -cyelohexyle- -1-aminc-2'.4di-methoxybenzene).s Brown mine 2 1aminobenzene-2-(carbonyl-diethyl-amine) -1-amino-4-ch1orobenzene) Do. 3 1-aminobenzene-2-(sulfonyl-n-dibutyl-amine) -aminobenzene) l Do. 4 1-aminobenzene-2-(carbonyl-dibenzyl-amine) -aminobenzene) vDo. 5 l-a1ninobenzene-2-(sullonyl-n-dibutyl-amine) -1 emn1ol-chlorobenzene Do. 6 1-aminobenzene-2-(carbonyl-diethyl-amine) L 3 hydroxydiphenylcne -'sulflde 2 (carbonyh Do.

, 'aminobenzene). 7 1-am1nobenzene-2-(sulfonylN-(n) -butyl-l' -amino-2 3-hydroxydiphenylene-ox1de-2(carbonyl-am1no- Do. methylbenzene). I benzene). I V 1 2-hydroxycarbazo1e-3-(carbonyl- I 8 1 amlrsob enzene 2 -(sulfonyl N -benzy1- cyclohexyla- -aminobenzene) Do. mine 1 9 1 amino 3 methylbenzene 6 -(carbonyl dimethyla- -aminobenzene) Do.

mine l0 1-a1iuino-33Inethylbenzene-6-(carbonyl-N-benzyl-phen- -aminobenzene) Do. y amine I r 11 lamino-3-methy1benzene-6-(ca.rbonyl-dicyclohexyla- -1-ami.no-2'.4-diniethoyxbenzene. is Do. mine v 12 l amino 3 lnethylbenzene 6 -(carbonyl diphenyla- -l-amino-2.5-dimethoxybenzene) Do.

mme Y I 13 1 ami.no 4 -chlorobenzene 6-(carbonyl -N -phenyl 2- l'-amino-2 .5-dimethoxybenzene) Do naphthylatnine). I 14 1-ami no-4-chlorobenzene-G-(carbonyl-N-carbazol e) 1 -am1nobenzene) Do. 15 1 ammo -4 phenoxybenzcne 6 -(carbonyl N -methyl- -aminobenzene) Do.

. benzylamine). 16 l amino 4 methoxybenzene 6 -(sulfonyln-dibutyla- -1 amino-4chlorobenzene) Do.

mule 17' l-amino-4-ethoxybenzene-6-(sulfonyl-n-dibutylamine) -2'-aminonaphthalene) Do. 18 l amlno 3 -methylbenzene 6 carbonyl n -dibutyla- -1-amino-4-chlorob enzene) Do. mm 19 1amino-3-n:1ethoXybenzene-6-(carbonyl-diethylamine)' -aminobenzene) Do. 20 l -an znn)o -4 -methoxybenzene 6 -(sulfonyl n -dibutyla- -1- am)in0- 3 -(diethylamino carbonyl ben- Do.

mine zene 21 Do -l-amino-2-(phenylsu1fonyl-benzene) Do. 22 l amino 3 methoxybenzene 6 -(carbonyl diethyla- -l'- am)ino- 3 -(ndibutylammosulfonyl ben-- Do.

mme A zene 23 1-amino-4-ethoxybenzene-6:(su1fonyl-n-dibutylamine) Q-methyl-Z-hydroxycarbazole-3-(carbonyl-1-am- Do.

I I ino-2-methyl-4-methoxybenzene) Since an objector the present invention is: to

" provide dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in'the appended claims do not contain any substituents which are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuffs t0 alkalies. substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

.I claim:

2. The water-insoluble mono-azo-dyestuffs of the following general formula:

wherein X means one of the groups CO- and -SO2, R1 and R: stand for members of the group consisting of alkyl, benzyl, radicals of the benzene and naphthalene series and lwdroaromatic radicals which may be connected in a heterocyclic ring system, with the proviso that if X stands for S02, R1 and R: may only be simultaneously alkyl radicals if the sum of their carbon atoms be at least 5, Z stands for a radical of the group consisting of carbazole, di-phenylene oxide and diphenylene sulfide and Y stands for a radical of the benzene series, being insoluble in water, but very easily soluble in organic solvents and yielding generally brown tints of good properties of fastness.

3. The water-insoluble mono-azo-dyestuff of the following formula:

being insoluble in water, but very easily soluble in organic solvents and yielding brown tints of good properties of fastness.

4. The water-insoluble mono-azo-dyestufi of the following formula:

If (34 900 N 15 being insoluble in water, but very easily soluble in organic solvents and yielding brown tints of good properties of fastness.

5. The water-insoluble mono-azo-dyestuff of the following formula:

being insoluble in water, but very easily soluble in organic solvents and yielding brown tints of good properties of fastness.

ERNST FISCHER. 

